Polymeric compounds



United 2,700,658 POLYMERIC CUM-POUNDS This application is a division of application Serial Number 272,245, filed February 1. 1952, for Polymeric Compounds, and of application Serial Number 634,394, filed December 11, 1945, for Polymer Polysulfides Containing Ether Groups now Patent 2,586,182.

My'invention relates to a new class of products and methods whereby they may be produced. More particularly, it relates to polyalkylene olysulfides having lateral ether groups and methods whereby they may be prepared.

In my copending application Serial Number 470,909 of December 31, 1942, now abandoned, polymeric ethylene polysulfides and a method whereby they may be prepared is disclosed. These compounds are useful for the preparation of coatings, impregnations, cementing materials,

and the like. They are also valuable as oil resistant rubber-like materials suitable for the manufacture of oil resistant hose. I have discovered that compounds having particular usefulness for the above mentioned purposes and which are suitable for convenient preparation are obtained when the polymeric ethylene polysulfides con tain lateral ether groups.

The polyalkylene polysulfides having lateral ether groups as contemplated in this invention have recurring structural units of the formula:

(OHz(|3HS,,-) p R where n is a small integer greater than 1, R a radical containing an ether group, and x is the number of recurring structural units in the polymer.

In accordance with another aspect of my invention the preparation of polyalkylene polysulfides having lateral ether groups is obtained by reaction of alkali metal polysulfide with a dihalogenoalky other, as illustrated by the equations:

BrCHa-CHBr-GHsO GB; N825 illustrated by the following examples:

Example 1.'A mixture of 232 parts (1 mol+%) of sodium sulfide (NazS.9HzO), 68 parts (2 mols+5%) of sulphur, and 90 parts of water is stirred at 50C. until all the sulphur is dissolved. To form magnesium hydroxide, which acts as a dispersing agent in the subsequent polymer formation, 12 parts of sodium hydroxlde are added, followed by the gradual addition with stirring of a solution of 30.6 parts of magnesium chloride (MgCl2.6H2O) in 40 parts of water. To the solution of sodium polysulfide maintained at about 50 C. 1s then added with stirring, over a period of 3 to 4 hours, 246 parts (1 mol) of 2,3-dibromopmpyl ethyl ether (prepared by brominating allyl ethyl ether n chloroform). The polymeric sulfide which separates is digested by stirring the reaction mixture at 7075 C. for 7 to 8 hours. Aft

the contents of the reaction vessel are poured t l a ge volume of water and the solid is washed with water by decantation until the supernatant layer becomes pale yellow, then air-dr ed.

Example 2.--A mixture or 252 parts of sodium sulfide (NasSSI-IzO) 68 parts of sulfur, and 90 parts of waatent lustration.

ter is stirred at 50 C. until all the sulfur is dissolved. 16 parts of sodium hydroxide are added, followed by the gradual addition with stirring of 41 parts of magnesium chloride (MgC1z.6H2O). To the solution of sodium polysulfide maintained at about 50 C. are then added with stirring, over a period of about 5 hours, 232 parts of 2,3-dibromopropyl methyl ether (prepared by brominating allyl methyl ether in chloroform). The resulting polymeric sulfide which separates is digested by stirring the reaction mixture at 70-75 C. for about 9 hours. After cooling, the polymeric sulfide is filtered from the reaction mixture, washed once with a mixture of equal parts of water and ethyl alcohol, and dried at reduced pressure in a desiccator at room temperature, 193 parts of polymeric product being obtained.

Example 3.A solution of sodium polysulfide containing magnesium hydroxide is prepared in the manner described in the preceding example from 134 parts of sodium sulfide (Na2S.9H2O), 35 parts of sulfur, 50 parts of water, 8 parts of sodium hydroxide, and 21 parts of magnesium chloride hexahydrate. To this solution, maintained at about 50 C., are added with stirring over a period of 2 hours, 132 parts of 2,3-dibromopropyl isopropyl ether (prepared by brominating allyl isopropyl ether in chloroform). The polymeric sulfide which separates is digested by stirring the reaction mixture for about 7 hours at 7075 C. After cooling, the contents of the reaction vessel are poured into water, the solid washed with water and air dried.

Example 4. A mixture of 264 parts of sodium sulfide (NazS.9HzO) and 71 parts of sulfur is melted together by stirring at 50 C. To this solution of sodium polysulfide, maintained at about 50 stirring, over a period of 5 hours, a solution of 274 parts of 2,3-dibromopropyl n-butyl ether (prepared by bromiuating allyl n-butyl ether in chloroform) in 198 parts of methanol. The reaction mixture is then stirred at 7075 C. for an additional 18 hours to complete the formation of the polymer. After standing at room temperature for about 16 hours, the polymeric sulfide separates from the reaction mixture as a clear tatr'y-like material. It is washed by trituration with water and then with methanol, and is finally dried in a desiccator at reduced pressure.

The above described processes are only by way of il- The polymeric alkoxyethylene polysulfides derived from the methyl, isopropyl, and n-butyl ethers of 2,3-dibromopropanol can be prepared by the process of the above examples. Polysulfides containing aromatic, alkyl-aromaticcycloaliphatic or heterocyclic other groups may also be prepared by generally similar processes from dihalogenoalkyl ethers having such groups attached to the ether oxygen atom.

My new polymeric alkylene polysulfides having lateral ether groups are viscous resins, insoluble in water but soluble in some organic solvents, as for example dioxane. They may be used as intermediates in the preparation of vicinal dimercapto ethers by catalytic hydrogenation in the presence of a sulf-active catalyst, such as cobalt sul fide. The preparation of such monomeric ethers is disclosed by A. A. Pavlic and W. J. Peppel in application Ser. No. 568,064, filed December 13, 1944, now Patent No. 2,397,698, issued April 2. 1946.

My invention is capable of wide variations from the f(1)11n described, its scope being defined in the appended 0 am.

What is claimed is:

The process of preparing a polvmeric (n-butoxymethyl)- ethylene polysulfide characterized by the steps of melting together sodium sulfide and sulfur in approximately the following proportions:

Parts Sodium sulfide (NazS.9I-Iz0) 264 Sulfur 71 No references cited.

C., is added dropwise with' 

